Polyanthrylene materials and methods for their preparation and use

ABSTRACT

Compositions containing polyanthrylene and methods of making these compositions are disclosed herein. The polyanthrylene composition can, for example, be used for detection of iron in a sample.

RELATED APPLICATIONS

The instant application is the U.S. National Phase under 35 U.S.C. §371 of International Application No. PCT/CN2011/072487 entitled POLYANTHRYLENE MATERIALS AND METHODS FOR THEIR PREPARATION AND USE, filed Apr. 7, 2011, designating the U.S. The content of this application is herein incorporated by reference in its entirety.

BACKGROUND

1. Field

The present application relates to compositions and methods for detecting iron in a sample.

2. Description of the Related Art

At present, the common methods used for iron determination include UV-vis spectrophotometry, atomic absorption spectrometry (AAS) and inductively coupled plasma mass spectrometry (ICP-MS). These methods have limited capacity in iron determination because of their inability to detect iron content below ppm level (10⁻⁶ M), high operation cost, and/or susceptibility to interference from common cations such as Na(I), Ca(II) and Mg(II). In addition, metal ions such as Cu(II) may interfere with detection of iron in chemosensors that utilize low-molecular organic compounds and polymers. There is a need for low-cost iron-sensitive detection methods with anti-interference capabilities.

SUMMARY

Some embodiments disclosed herein include a composition having one or more polyanthrylenes, wherein the one or more polyanthrylenes each independently comprises at least two monomer units represented by a formula selected from the group consisting of Formula I, Formula II, Formula III, Formula IV, Formula V, Formula VI, Formula VII, Formula VIII, Formula IX, Formula X, Formula XI, Formula XII, Formula XIII, Formula XIV, Formula XV, Formula XVI, Formula XVII, and any combination thereof:

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷, R³⁸, R³⁹, R⁴⁰, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷, R⁴⁸, R⁴⁹, R⁵⁰, R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷, R⁵⁸, R⁵⁹, R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, R⁶⁶, R⁶⁷, and R⁶⁸ are each independently hydrogen or an electron donating group; and

-   -   wherein at least one monomer unit in the composition is not         represented by Formula I.

In some embodiments, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷, R³⁸, R³⁹, R⁴⁰, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷, R⁴⁸, R⁴⁹, R⁵⁰, R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷, R⁵⁸, R⁵⁹, R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, R⁶⁶, R⁶⁷, and R⁶⁸ are each independently hydrogen. In some embodiments, the electron donating group is selected from the group consisting of —CH₃, —CH₂CH₃, —OH, —OCH₃, —OCH₂CH₃, —N(CH₃)₂, —N(CH₂CH₃)₂, and —SH.

In some embodiments, at least one of the one or more polyanthrylenes comprises at least three anthracene units each independently represented by a formula selected from the group consisting of Formula I, Formula II, Formula III, Formula IV, Formula V, Formula VI, Formula VII, Formula VIII, Formula IX, Formula X, Formula XI, Formula XII, Formula XIII, Formula XIV, Formula XV, Formula XVI, and Formula XVII, and any combination thereof. In some embodiments, at least one of the one or more polyanthrylenes has a molecular formula selected from the group consisting of C₄₂H₂₂, C₅₆H₃₀, C₇₀H₂₆, C₁₂₆H₆₈, C₁₄₀C₇₈, and C₁₅₄H₈₄. In some embodiments, at least one of the one or more polyanthrylenes has a molecular formula of C₄₂H₂₂. In some embodiments, at least one of the one or more polyanthrylenes includes a compound represented by Formula XVIII or Formula XIX:

In some embodiments, at least one of the one or more polyanthrylenes has a molecular formula of C₅₆H₃₀. In some embodiments, at least one of the one or more polyanthrylenes includes a compound represented by a formula selected from the group consisting of Formula XX, Formula XXI, Formula XXII, and Formula XXIII:

In some embodiments, at least one of the one or more polyanthrylenes has a molecular formula of C₇₀H₁₆. In some embodiments, at least one of the one or more polyanthrylenes has a molecular formula of C₁₂₆H₆₈. In some embodiments, at least one of the one or more polyanthrylenes has a molecular formula of C₁₄₀H₇₈. In some embodiments, at least one of the one or more polyanthrylenes has a molecular formula of C₁₅₄H₈₄. In some embodiments, at least one of the one or more polyanthrylenes includes a compound represented by Formula XXIV:

wherein n is an integer from 1 to 11.

In some embodiments, the composition comprises at least 1 ppm of the one or more polyanthrylenes. In some embodiments, the composition exhibits a peak emission wavelength of about 380 nm to about 650 nm when exposed to ultraviolet or violet radiation. In some embodiments, the average molecular weight of the one or more polyanthrylenes is from about 526 g/mol to about 1932 g/mol. In some embodiments, the average molecular weight of the one or more polyanthrylenes is from about 526 g/mol to about 868 g/mol.

Some embodiments disclosed herein include a method of making a copolymer, the method includes: forming a composition comprising at least one oxidizing agent, at least one co-catalyst and anthracene; and maintaining the composition under conditions effective to covalently bond two or more anthracenes to form one or more polyanthrylenes. In some embodiments, the one or more polyanthrylenes each independently comprises at least two monomer units each independently represented by a formula selected from the group consisting of Formula I, Formula II, Formula III, Formula IV, Formula V, Formula VI, Formula VII, Formula VIII, Formula IX, Formula X, Formula XI, Formula XII, Formula XIII, Formula XIV, Formula XV, Formula XVI, Formula XVII, and any combination thereof:

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷, R³⁸, R³⁹, R⁴⁰, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷, R⁴⁸, R⁴⁹, R⁵⁰, R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷, R⁵⁸, R⁵⁹, R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, R⁶⁶, R⁶⁷, and R⁶⁸ are each independently hydrogen or an electron donating group; and

wherein at least one monomer unit in the composition is not represented by Formula I.

In some embodiments, the molar ratio of the oxidizing agent to anthracene in the composition is less than or equal to about 18:1. In some embodiments, the molar ratio of the oxidizing agent to anthracene in the composition is from about 7:1 to about 9:1. In some embodiments, the oxidizing agent is a Lewis acid. In some embodiments, the Lewis acid is selected from the group consisting of FeCl₃, AlCl₃—CuCl₂, TiCl₄, MoCl₅, SbCl₅, AsF₅, and any combination thereof. In some embodiments, the co-catalyst is selected from the group consisting of nitro-alkanes, halogenated alkanes and alkanes. In some embodiments, the co-catalyst is selected from the group consisting of CH₃NO₂, CH₂Cl₂, n-hexane, CH₃CH₂NO₂ and CH₃CH₂Cl₂. In some embodiments, the co-catalyst is CH₃NO₂, CH₂Cl₂ or n-hexane. In some embodiments, the maintaining step is performed at a temperature of about 10° C. to about 80° C. In some embodiments, at least one of the one or more polyanthrylenes has a molecular formula selected from the group consisting of C₄₂H₂₂, C₅₆H₃₀, C₇₀H₂₆, C₁₂₆H₆₈, C₁₄₀H₇₈, and C₁₅₄H₈₄. In some embodiments, at least about 90% by weight of a total amount of aromatic organic compounds in the composition are polyanthrylene.

Some embodiments disclosed herein include an apparatus including: at least one light source configured to emit an ultraviolet or violet radiation, and a composition configured to receive at least a portion of the radiation emitted from the light source, wherein the composition comprises one or more polyanthrylenes, wherein the one or more polyanthrylenes each independently comprises at least two monomer units each independently represented by a formula selected from the group consisting of Formula I, Formula II, Formula III, Formula IV, Formula V, Formula VI, Formula VII, Formula VIII, Formula IX, Formula X, Formula XI, Formula XII, Formula XIII, Formula XIV, Formula XV, Formula XVI, Formula XVII, and any combination thereof:

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷, R³⁸, R³⁹, R⁴⁰, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷, R⁴⁸, R⁴⁹, R⁵⁰, R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷, R⁵⁸, R⁵⁹, R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, R⁶⁶, R⁶⁷, and R⁶⁸ are each independently hydrogen or an electron donating group; and

wherein at least one monomer unit in the composition is not represented by Formula I.

In some embodiments, the apparatus further comprises at least one light detector configured to measure light emitted from the composition. In some embodiments, the apparatus further comprises a housing, wherein the housing contains the composition and is configured to receive a sample adjacent to the composition.

Some embodiments disclosed herein include a method for detecting ferric ions from a sample, the method includes: providing a sample suspected of containing one or more ferric ions; and contacting the sample with a composition to form a mixture, wherein the composition comprises one or more polyanthrylenes, wherein the one or more polyanthrylenes each independently comprises at least two monomer units each independently represented by a formula selected from the group consisting of Formula I, Formula II, Formula III, Formula IV, Formula V, Formula VI, Formula VII, Formula VII, Formula IX, Formula X, Formula XI, Formula XII, Formula XIII, Formula XIV, Formula XV, Formula XVI, Formula XVII, and any combination thereof:

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷, R³⁸, R³⁹, R⁴⁰, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷, R⁴⁸, R⁴⁹, R⁵⁰, R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷, R⁵⁸, R⁵⁹, R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, R⁶⁶, R⁶⁷, and R⁶⁸ are each independently hydrogen or an electron donating group, and wherein at least one monomer unit in the composition is not represented by Formula I;

exposing the mixture to a radiation effective to produce fluorescence from the composition; and

measuring the amount of fluorescence produced by the mixture

In some embodiments, the produced fluorescence is greater in the absence of ferric ions than in the presence of ferric ions. In some embodiments, the concentration of the ferric ions in the sample is from about 10⁻³ M to about 10⁻⁹ M. In some embodiments, the concentration of the ferric ions in the sample is from about 10⁻⁶ M to about 10⁻⁹ M.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts an illustrative embodiment of a lighting apparatus that is within the scope of the present application (not to scale).

FIG. 2 depicts an illustrative embodiment of an apparatus for detecting ferric ions that is within the scope of the present application (not to scale).

FIG. 3 depicts an illustrative embodiment of an apparatus for detecting ferric ions that is within the scope of the present application (not to scale).

FIG. 4 a-c shows the UV-visible, fluorescence excitation and emission spectra of anthracene (An) and polyanthrylene (PAn) solutions in NMP at concentration of 20 mg/L.

FIG. 5 shows the MALDI-TOF mass spectra for the polyanthrylene (PAn) prepared with FeCl₃/An molar ratio of 9:1.

FIG. 6 a-c shows the NMR spectra of An and PAn. FIG. 6 a shows the 400 MHz ¹H—¹H COSY spectra of An; FIG. 6 b shows the 400 MHz ¹H-¹H COSY spectra of soluble part of the PAn; FIG. 6 c shows 500 MHz ¹H-NMR spectra of An and soluble part of the PAn in DMSO-d6. The arrows in FIG. 6 c represent the correlation of two types of adjacent hydrogen protons.

FIG. 7 shows fluorescence emission spectra (excited at 380 nm) of the PAn in NMP at various concentrations.

FIG. 8 shows fluorescent emission spectra of the PAn-NMP solutions containing three water contents.

FIG. 9 shows fluorescence emission spectra (excited at 380 nm) for the same PAn solution after adding various aqueous solutions with different Fe(III) content. Inset: the modified Stern-Volmer plot. I₀ and I represent the emission intensities at 502 nm without and with the Fe(III) quencher, respectively.

FIG. 10 a-b shows fluorescence emission spectra (a), and fluorescence quenching efficiencies and metal-ion charge density (b) of the same PAn solution (PAn at concentration 20 mg/L) containing 1 mM different aqueous metal ions. I₀ and I refer to the emission intensity at 502 nm before and after adding metal ions.

FIG. 11 a-b shows fluorescent emission spectra of various PAn-NMP solutions (PAn at concentration 20 mg/L) with different content in metal ions.

DETAILED DESCRIPTION

In the following detailed description, reference is made to the accompanying drawings, which form a part hereof. In the drawings, similar symbols typically identify similar components, unless context dictates otherwise. The illustrative embodiments described in the detailed description, drawings, and claims are not meant to be Limiting. Other embodiments may be utilized, and other changes may be made, without departing from the spirit or scope of the subject matter presented herein. It will be readily understood that the aspects of the present disclosure, as generally described herein, and illustrated in the Figures, can be arranged, substituted, combined, separated, and designed in a wide variety of different configurations, all of which are explicitly contemplated herein.

Disclosed herein are compounds including one or more polyanthrylene. These compounds may, for example, exhibit superior fluorescence properties. The compounds may also provide, in some embodiments, highly sensitive detection of iron, such as ferric ions. The present application also relates to methods of making these compounds, method of using these compounds, and apparatuses that include these compounds.

DEFINITIONS

As used herein, the term “electron donating” refers to the ability of a substituent to donate electrons relative to that of hydrogen if the hydrogen atom occupied the same position in the molecule. This term is well understood by one skilled in the art and discussed in Advanced Organic Chemistry by M. Smith and J. March, John Wiley and Sons, New York N.Y. (2007). Non-limiting examples of electron donating group include —CH₃, —CH₂CH₃, —OH, —OCH₃, —OCH₂CH₃, —N(CH₃)₂, —N(CH₂CH₃)₂, and —SH.

Compositions Including Polyanthrylene

Some embodiments disclosed herein include a composition having one or more polyanthrylenes, wherein the one or more polyanthrylenes each independently comprises at least two monomer units represented by a formula selected from the group consisting of Formula I, Formula II, Formula III, Formula IV, Formula V, Formula VI, Formula VII, Formula VIII, Formula IX, Formula X, Formula XI, Formula XII, Formula XIII, Formula XIV, Formula XV, Formula XVI, Formula XVII, and any combination thereof:

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷, R³⁸, R³⁹, R⁴⁰, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷, R⁴⁸, R⁴⁹, R⁵⁰, R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷, R⁵⁸, R⁵⁹, R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, R⁶⁶, R⁶⁷, and R⁶⁸ are each independently hydrogen or an electron donating group; and

-   -   wherein at least one monomer unit in the composition is not         represented by Formula I.

In some embodiments, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷, R³⁸, R³⁹, R⁴⁰, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷, R⁴⁸, R⁴⁹, R⁵⁰, R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷, R⁵⁸, R⁵⁹, R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, R⁶⁶, R⁶⁷, and R⁶⁸ are hydrogen. Examples of electron donating group include, but are not limited, to —CH₃, —CH₂CH₃, —OH, —OCH₃, —OCH₂CH₃, —N(CH₃)₂, —N(CH₂CH₃)₂, and —SH. In some embodiments, the electron donating group does not include —NH₂, —NHCH₃ and —NHCH₂CH₃.

For purposes of the present application, the nomenclature for anthracene units with the polyanthrylene is shown below:

As noted above, the polyanthrylene can include two or more anthracene units. The two anthracene units can be linked together to form the polyanthrylene. In some embodiments, the polyanthrylene includes at least two anthracene units that are covalently bonded together by one or more carbon-carbon bonds. For example, a polyanthrylene can include two anthracene units with a covalent bond between the 5- and the 8-positions, the 10- and the 9-positions, or the 1- and the 4-positions on the respective anthracene unit.

In some embodiments, at least a portion of the anthracene units (e.g., two, three, four, five, six, seven, eight, nine, ten or more anthracene units) in the polyanthrylene each have one, two, or more carbon-carbon bonds linking with one or more anthracene units. In some embodiments, all of the anthracene units in the polyanthrylene each include, one, two, or more carbon-carbon bonds linking with at least one other anthracene unit. As one example, the polyanthrylene represented by Formula XVIII includes one anthracene unit that include carbon-carbon bonds at the 8- and 9-positions which link to one other anthracene unit, one anthracene unit that includes carbon-carbon bonds at the 5-, 10-, 8- and 9-positions which link to two other anthracene units, and one anthracene unit that includes carbon-carbon bonds at the 5- and 10-positions which link to one other anthracene unit.

As another example, the polyanthrylene represented by Formula XIX includes one anthracene unit that include carbon-carbon bonds at the 8- and 9-positions which link to one other anthracene unit, one anthracene unit that includes carbon-carbon bonds at the 5-, 10-, 9- and 4-positions which link to two other anthracene units, and one anthracene unit that includes carbon-carbon bonds at the 10- and 1-positions which link to one other anthracene unit.

As still another example, the polyanthrylene represented by Formula XX includes one anthracene unit that includes carbon-carbon bonds at the 8- and 9-positions which link to one other anthracene unit, one anthracene unit that includes carbon-carbon bonds at the 5-, 10-, 8- and 9-positions which link to two other anthracene units, one anthracene unit that includes carbon-carbon bonds at the 5-, 10- and 9-positions which link to two other anthracene units, and one anthracene unit that includes a carbon-carbon bond at the 10-position which links to one other anthracene unit.

As yet another example, the polyanthrylene represented by Formula XXI includes one anthracene unit that includes carbon-carbon bonds at the 8- and 9-positions which link to one other anthracene unit, one anthracene unit that includes carbon-carbon bonds at the 5-, 10-, 9- and 4-positions which link to two other anthracene units, one anthracene unit that includes carbon-carbon bonds at the 10-, 1- and 9-positions which link to two other anthracene units, and one anthracene unit that includes a carbon-carbon bond at the 10-position which links to one other anthracene unit.

As yet still another example, the polyanthrylene represented by Formula XXII includes one anthracene unit that includes carbon-carbon bonds at the 8- and 9-positions which link to one other anthracene unit, one anthracene unit that includes carbon-carbon bonds at the 5-, 10- and 9-positions which link to two other anthracene units, one anthracene unit that includes carbon-carbon bonds at the 10-, 8- and 9-positions which link to two other anthracene units, and one anthracene unit that includes carbon-carbon bonds at the 5- and 10-position which links to one other anthracene unit.

As another example, the polyanthrylene represented by Formula XXIII includes one anthracene unit that includes carbon-carbon bonds at the 8- and 9-positions which link to one other anthracene unit, one anthracene unit that includes carbon-carbon bonds at the 5-, 10- and 9-positions which link to two other anthracene units, one anthracene unit that includes carbon-carbon bonds at the 10-, 9- and 4-positions which link to two other anthracene units, and one anthracene unit that includes carbon-carbon bonds at the 10- and 1-position which links to one other anthracene unit.

In some embodiments, at least a portion of the anthracene units (e.g., one, two, three, four, five, six, seven, or more of the anthracene units) in the polyanthrylene each include one or two carbon-carbon bonds linking with one or two other anthracene units. In some embodiments, all of the anthracene units in the polyanthrylene each include one or two carbon-carbon bonds linking with one or two other anthracene units. In some embodiments, at least a portion of the anthracene units in the polyanthrylene each include two carbon-carbon bonds linking with one or two other anthracene units. In some embodiments, at least a portion of the anthracene units in the polyanthrylene each include three carbon-carbon bonds linking with one or two other anthracene units. In some embodiments, at least a portion of the anthracene units in the polyanthrylene each include four, five or six carbon-carbon bonds linking with two other anthracene units.

In some embodiments, at least a portion of the anthracene units (e.g., one, two, three, four, five, six, seven, or more of the anthracene units) in the polyanthrylene each include two or more carbon-carbon bonds linking with one, two, or more other anthracene units, where each carbon-carbon bond is attached on each anthracene unit at a carbon position independently selected from 1, 4, 5, 8, 9, and 10.

In some embodiments, at least a portion of the anthracene units (e.g., one, two, three, four, five, six, seven, or more of the anthracene units) in the polyanthrylene each include two carbon-carbon bonds linking with two other anthracene units, where each carbon-carbon bond is attached on each anthracene unit at a carbon position independently selected from 10 and 9. As one example, the polyanthrylene can include one or more anthracene units represented by Formula I:

In some embodiments, at least a portion of the anthracene units (e.g., one, two, three, four, five, six, seven, or more of the anthracene units) in the polyanthrylene each include two carbon-carbon bonds linking with two other anthracene units, where each carbon-carbon bond is attached on each anthracene unit at a carbon position independently selected from 1 and 4. As one example, the polyanthrylene can include one or more anthracene units represented by Formula II:

In some embodiments, at least a portion of the anthracene units (e.g., one, two, three, four, five, six, seven, or more of the anthracene units) in the polyanthrylene each include four carbon-carbon bonds linking with two other anthracene units, where each carbon-carbon bond is attached on each anthracene unit at a carbon position independently selected from 5, 8, 10, and 9. As one example, the polyanthrylene can include one or more anthracene units represented by Formula III:

In some embodiments, at least a portion of the anthracene units (e.g., one, two, three, four, five, six, seven, or more of the anthracene units) in the polyanthrylene each include six carbon-carbon bonds linking with two other anthracene units, where each carbon-carbon bond is attached on each anthracene unit at a carbon position independently selected from 5, 8, 10, 9, 1, and 4. As one example, the polyanthrylene can include one or more anthracene units represented by Formula IV:

In some embodiments, at least a portion of the anthracene units (e.g., one, two, three, four, five, six, seven, or more of the anthracene units) in the polyanthrylene each include two carbon-carbon bonds linking with two other anthracene units, where each carbon-carbon bond is attached on each anthracene unit at a carbon position independently selected from 10 and 4. As one example, the polyanthrylene can include one or more anthracene units represented by Formula V:

In some embodiments, at least a portion of the anthracene units (e.g., one, two, three, four, five, six, seven, or more of the anthracene units) in the polyanthrylene each include three carbon-carbon bonds linking with two other anthracene units, where each carbon-carbon bond is attached on each anthracene unit at a carbon position independently selected from 10, 9 and 4. As one example, the polyanthrylene can include one or more anthracene units represented by Formula VI:

In some embodiments, at least a portion of the anthracene units (e.g., one, two, three, four, five, six, seven, or more of the anthracene units) in the polyanthrylene each include four carbon-carbon bonds linking with two other anthracene units, where each carbon-carbon bond is attached on each anthracene unit at a carbon position independently selected from 10, 8, 9 and 4. As one example, the polyanthrylene can include one or more anthracene units represented by Formula VII:

In some embodiments, at least a portion of the anthracene units (e.g., one, two, three, four, five, six, seven, or more of the anthracene units) in the polyanthrylene each include two carbon-carbon bonds linking with two other anthracene units, where each carbon-carbon bond is attached on each anthracene unit at a carbon position independently selected from 1 and 9. As one example, the polyanthrylene can include one or more anthracene units represented by Formula VIII:

In some embodiments, at least a portion of the anthracene units (e.g., one, two, three, four, five, six, seven, or more of the anthracene units) in the polyanthrylene each include three carbon-carbon bonds linking with two other anthracene units, where each carbon-carbon bond is attached on each anthracene unit at a carbon position independently selected from 1, 9 and 4. As one example, the polyanthrylene can include one or more anthracene units represented by Formula IX:

In some embodiments, at least a portion of the anthracene units (e.g., one, two, three, four, five, six, seven, or more of the anthracene units) in the polyanthrylene each include three carbon-carbon bonds linking with two other anthracene units, where each carbon-carbon bond is attached on each anthracene unit at a carbon position independently selected from 1, 8 and 9. As one example, the polyanthrylene can include one or more anthracene units represented by Formula X:

In some embodiments, at least a portion of the anthracene units (e.g., one, two, three, four, five, six, seven, or more of the anthracene units) in the polyanthrylene each include four carbon-carbon bonds linking with two other anthracene units, where each carbon-carbon bond is attached on each anthracene unit at a carbon position independently selected from 1, 8, 9, and 4. As one example, the polyanthrylene can include one or more anthracene units represented by Formula XI:

In some embodiments, at least a portion of the anthracene units (e.g., one, two, three, four, five, six, seven, or more of the anthracene units) in the polyanthrylene each include three carbon-carbon bonds linking with two other anthracene units, where each carbon-carbon bond is attached on each anthracene unit at a carbon position independently selected from 10, 1 and 9. As one example, the polyanthrylene can include one or more anthracene units represented by Formula XII:

In some embodiments, at least a portion of the anthracene units (e.g., one, two, three, four, five, six, seven, or more of the anthracene units) in the polyanthrylene each include three carbon-carbon bonds linking with two other anthracene units, where each carbon-carbon bond is attached on each anthracene unit at a carbon position independently selected from 10, 1 and 4. As one example, the polyanthrylene can include one or more anthracene units represented by Formula XIII:

In some embodiments, at least a portion of the anthracene units (e.g., one, two, three, four, five, six, seven, or more of the anthracene units) in the polyanthrylene each include three carbon-carbon bonds linking with two other anthracene units, where each carbon-carbon bond is attached on each anthracene unit at a carbon position independently selected from 10, 1 and 8. As one example, the polyanthrylene can include one or more anthracene units represented by Formula XIV:

In some embodiments, at least a portion of the anthracene units (e.g., one, two, three, four, five, six, seven, or more of the anthracene units) in the polyanthrylene each include five carbon-carbon bonds linking with two other anthracene units, where each carbon-carbon bond is attached on each anthracene unit at a carbon position independently selected from 10, 1, 8, 9 and 4. As one example, the polyanthrylene can include one or more anthracene units represented by Formula XV:

In some embodiments, at least a portion of the anthracene units (e.g., one, two, three, four, five, six, seven, or more of the anthracene units) in the polyanthrylene each include four carbon-carbon bonds linking with two other anthracene units, where each carbon-carbon bond is attached on each anthracene unit at a carbon position independently selected from 5, 10, 1, and 4. As one example, the polyanthrylene can include one or more anthracene units represented by Formula XVI:

In some embodiments, at least a portion of the anthracene units (e.g., one, two, three, four, five, six, seven, or more of the anthracene units) in the polyanthrylene each include five carbon-carbon bonds linking with two other anthracene units, where each carbon-carbon bond is attached on each anthracene unit at a carbon position independently selected from 5, 10, 1, 9, and 4. As one example, the polyanthrylene can include one or more anthracene units represented by Formula XVII:

The one or more polyanthrylenes in the composition can, in some embodiments, be selected from compounds represented by the chemical formula C_(14m)H_(10m-2x), where m is an integer greater than one (e.g., 2, 3, 4, 5, or more), and x is an integer that is greater than or equal to (m−1) and is less than or equal to 3(m−1) (i.e., m−1≦x≦3(m−1)). In some embodiments, m can be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15. In some embodiments, m can be 3, 4, 5, 6, 7, 8, 9, 10, or 11. In some embodiments, m can be 3, 4 or 5. Non-limiting examples of chemical formulas that can represent one or more polyanthrylenes in the composition include C₂₈H₁₆, C₂₈H₁₄, C₄₂H₂₄, C₄₂H₂₂, C₁₂H₂₀, C₄₂H₁₈, C₅₆H₃₂, C₅₆H₃₀, C₅₆H₂₈, C₅₆H₂₆, C₅₆H₂₄, C₅₆H₂₂, C₇₀H₄₀, C₇₀H₃₈, C₇₀H₃₆, C₇₀H₃₄, C₇₀H₃₂, C₇₀H₃₀, C₇₀H₂₈, C₇₀H₂₆, C₈₄H₄₈, C₈₄H₄₆, C₈₄H₄₄, C₈₄H₄₂, C₈₄H₄₀, C₈₄H₃₈, C₈₄H₃₆, C₈₄H₃₄, C₈₄H₃₂, C₈₄H₃₀, C₉₈H₅₆, C₉₈H₅₄, C₉₈H₅₂, C₉₈H₅₀, C₉₈H₄₈, C₉₈H₄₆, C₉₈H₄₄, C₉₈H₄₂, C₉₈H₄₀, C₉₈H₃₈, C₉₈H₃₆, C₉₈H₃₄, C₁₁₂H₆₄, C₁₁₂H₆₂, C₁₁₂H₆₀, C₁₁₂H₅₈, C₁₁₂H₅₆, C₁₁₂H₅₄, C₁₁₂H₅₂, C₁₁₂H₅₀, C₁₁₂H₄₈, C₁₁₂H₄₆, C₁₁₂H₄₄, C₁₁₂H₄₂, C₁₁₂H₄₀, C₁₁₂H₃₈, C₁₂₆H₇₂, C₁₂₆H₇₀, C₁₂₆H₆₈, C₁₂₆H₆₆, C₁₂₆H₆₄, C₁₂₆H₆₂, C₁₂₆H₆₀, C₁₂₆H₅₈, C₁₂₆H₅₆, C₁₂₆H₅₄, C₁₂₆H₅₂, C₁₂₆H₅₀, C₁₂₆H₄₈, C₁₂₆H₄₆, C₁₂₆H₄₄, C₁₂₆H₄₂, C₁₄₀H₈₀, C₁₄₀H₇₈, C₁₄₀H₇₆, C₁₄₀H₇₄, C₁₄₀H₇₂, C₁₄₀H₇₀, C₁₄₀H₆₈, C₁₄₀H₆₆, C₁₄₀H₆₄, C₁₄₀H₆₂, C₁₄₀H₆₀, C₁₄₀H₅₈, C₁₄₀H₅₆, C₁₄₀H₅₄, C₁₄₀H₅₂, C₁₄₀H₅₀, C₁₄₀H₄₈, C₁₄₀H₄₆, C₁₅₄H₈₈, C₁₅₄H₈₆, C₁₅₄H₈₄, C₁₅₄H₈₂, C₁₅₄H₈₀, C₁₅₄H₇₈, C₁₅₄H₇₆, C₁₅₄H₇₄, C₁₅₄H₇₂, C₁₅₄H₇₀, C₁₅₄H₆₈, C₁₅₄H₆₆, C₁₅₄H₆₄, C₁₅₄H₆₂, C₁₅₄H₆₀, C₁₅₄H₅₈, C₁₅₄H₅₆, C₁₅₄H₅₄, C₁₅₄H₅₂ and C₁₅₄H₅₀. In some embodiments, one or more polyanthrylenes in the composition can be represented by chemical formulas such as C₄₂H₂₂, C₅₆H₃₀, C₇₀H₂₆, C₁₂₆H₆₈, C₁₄₀H₇₈, and C₁₅₄H₈₄. In some embodiments, one or more polyanthrylenes in the composition can be represented by chemical formula XXIV, where n is an integer from 1 to 11.

The total amount of anthracene units in each polyanthrylene can vary. Each polyanthrylene can include, for example, two, three, four, five, six, seven, or more anthracene units. In some embodiments, only anthracene units are incorporated into the polyanthrylene. That is, no other monomer units, such as pyrrole, are linked (e.g., covalently bonded) with the anthracene units in the polyanthrylene. In some embodiments, the polyanthrylene consists of anthracene units.

The total amount of the one or more polyanthrylenes in the composition is not particularly limited and can vary depending upon the desired use. For example, a relatively small amount of one or more polyanthrylenes can be used for certain applications to detect iron ions that are discussed further below. The total amount of the one or more polyanthrylenes may, for example, be at least about 1 ppm; at least about 10 ppm; at least about 20 ppm; at least about 50 ppm; at least about 1% by weight; at least about 2% by weight; or at least about 5% by weight. The total amount of the one or more polyanthrylenes in the composition may, for example, be less than or equal to about 100% by weight, less than or equal to about 99% by weight; less than or equal to about 90% by weight; less than or equal to about 70% by weight; less than or equal to about 50% by weight; less than or equal to about 30% by weight; less than or equal to about 10% by weight; less than or equal to about 1% by weight; less than or equal to about 500 ppm. In some embodiments, the total amount of the one or more polyanthrylene in the composition is about 20 ppm.

In some embodiments, the average molecular weight of the one or more polyanthrylenes is from about 526 g/mol to about 1932 g/mol. In some embodiments, the average molecular weight of the one or more polyanthrylenes is from about 526 g/mol to about 868 g/mol.

It will be appreciated that the “total amount” of the one or more polyanthrylenes can include the combined amount of two or more different polyanthrylene compounds. For example, the total amount of the one or more polyanthrylenes can be the combined amount of polyanthrylenes represented by the chemical formulas C₄₂H₂₂ and C₅₆H₃₀. The total amount of the one or more polyanthrylenes can also be expressly limited to one or more specific compounds (or a sub-genus of compounds) disclosed in the present application.

In some embodiments, the one or more polyanthrylenes that can be in the composition include a compound represented by Formula XVIII, a compound represented by Formula XIX, a compound represented by Formula XX, a compound of Formula XXI, a compound of Formula XXII, a compound of Formula XXIII, a compound of Formula XXV, a compound of Formula XXVI, a compound of Formula XXVII, and a compound of Formula XXVIII:

The composition can also include, in some embodiments, two or more (e.g., two, three, four, or more) polyanthrylenes. The two or more polyanthrylenes can be any of those disclosed in the present application. For example, the composition can include a compound represented by Formula XX and a compound represented by Formula XXI. In some embodiments, the composition includes two or more (e.g., two, three, four, or more) polyanthrylenes that are each compounds represented by different chemical formulas. The chemical formulas can be, for example, two or more selected from C₂₈H₁₆, C₂₈H₁₄, C₄₂H₂₄, C₄₂H₂₂, C₄₂H₂₀, C₄₂H₁₈, C₅₆H₃₂, C₅₆H₃₀, C₅₆H₁₈, C₅₆H₆, C₅₆H₄, C₅₆H₂₂, C₇₀H₄₀, C₇₀H₃₈, C₇₀H₃₆, C₇₀H₃₄, C₇₀H₃₂, C₇₀H₃₀, C₇₀H₂₈, C₇₀H₂₆, C₈₄H₄₈, C₈₄H₄₆, C₈₄H₄₄, C₈₄H₄₂, C₈₄H₄₀, C₈₄H₃₈, C₈₄H₃₆, C₈₄H₃₄, C₈₄H₃₂, C₈₄H₃₀, C₉₈H₅₆, C₉₈H₅₄, C₉₈H₅₂, C₉₈H₅₀, C₉₈H₄₈, C₉₈H₄₆, C₉₈H₄₄, C₉₈H₄₂, C₉₈H₄₀, C₉₈H₃₈, C₉₈H₃₆, C₉₈H₃₄, C₁₁₂H₆₄, C₁₁₂H₆₂, C₁₁₂H₆₀, C₁₁₂H₅₈, C₁₁₂H₅₆, C₁₁₂H₅₄, C₁₁₂H₅₂, C₁₁₂H₅₀, C₁₁₂H₄₈, C₁₁₂H₄₆, C₁₁₂H₄₄, C₁₁₂H₄₂, C₁₁₂H₄₀, C₁₁₂H₃₈, C₁₂₆H₇₂, C₁₂₆H₇₀, C₁₂₆H₆₈, C₁₂₆H₆₆, C₁₂₆H₆₄, C₁₂₆H₆₂, C₁₂₆H₆₀, C₁₂₆H₅₈, C₁₂₆H₅₆, C₁₂₆H₅₄, C₁₂₆H₅₂, C₁₂₆H₅₀, C₁₂₆H₄₈, C₁₂₆H₄₆, C₁₂₆H₄₄, C₁₂₆H₄₂, C₁₄₀H₈₀, C₁₄₀H₇₈, C₁₄₀H₇₆, C₁₄₀H₇₄, C₁₄₀H₇₂, C₁₄₀H₇₀, C₁₄₀H₆₈, C₁₄₀H₆₆, C₁₄₀H₆₄, C₁₄₀H₆₂, C₁₄₀H₆₀, C₁₄₀H₅₈, C₁₄₀H₅₆, C₁₄₀H₅₄, C₁₄₀H₅₂, C₁₄₀H₅₀, C₁₄₀H₄₈, C₁₄₀H₄₆, C₁₅₄H₈₈, C₁₅₄H₈₆, C₁₅₄H₈₄, C₁₅₄H₈₂, C₁₅₄H₈₀, C₁₅₄H₇₈, C₁₅₄H₇₆, C₁₅₄H₇₄, C₁₅₄H₇₂, C₁₅₄H₇₀, C₁₅₄H₆₈, C₁₅₄H₆₆, C₁₅₄H₆₄, C₁₅₄H₆₂, C₁₅₄H₆₀, C₁₅₄H₅₈, C₁₅₄H₅₆, C₁₅₄H₅₄, C₁₅₄H₅₂ and C₁₅₄H₅₀. In some embodiments, the composition includes two or more (e.g., two, three, four, or more) polyanthrylenes that are each different compounds selected from a compound represented by Formula XVIII, a compound represented by Formula XIX, a compound represented by Formula XX, a compound of Formula XXI, a compound of Formula XXII, a compound of Formula XXIII, a compound of Formula XXV, a compound of Formula XXVI, a compound of Formula XXVII, and a compound of Formula XXVIII.

The composition can be in the form of a liquid that includes the one or more polyanthrylenes. For example, the one or more polyanthrylenes can be dispersed or dissolved in a solvent. The solvent can be an organic solvent or water. The organic solvent may, for example, be a non-polar solvent, a polar aprotic solvent, a polar protic solvent, or combinations thereof. In some embodiments, the composition includes a polar aprotic solvent. Non-limiting examples of polar aprotic solvents include n-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMA) and dimethyl sulfoxide (DMS). The amount of solvent in the composition can be, for example, at least about 95% by weight; at least about 99% by weight; at least about 99.5% by weight; or at least about 99.9% by weight. The concentration of the one or more polyanthrylenes in the composition can be, for example, about 1 mg/L to about 200 mg/L; about 5 mg/L to about 120 mg/L; about 10 mg/L to about 90 mg/L; about 20 mg/L to about 70 mg/L; or about 40 mg/L to about 60 mg/L.

The composition may, in some embodiments, be in the form of a solid. For example, a solid form of the polyanthrylene can be obtained by precipitating or drying the polyanthrylene from solution (e.g., solvent casting). The solid composition can include amorphous or semi-crystalline forms of the polyanthrylene. In some embodiments, the one or more polyanthrylenes are blended with one or more polymers. Generally, any inert polymer can be blended with the polyanthrylenes; such inert polymers can be, for example, acrylics, polyolefins, polyamides, polyesters, polysulfones, fluoropolymers, vinyl polymers, and the like. For example, the composition can be a blend of a compound of Formula XVIII and polysulfone. This blend can by prepared, for example, by solvent casting to form a film. The amount of the polymer in the composition is not particularly limited and can be, for example, at least about 10% by weight; at least about 30% by weight; at least about 70% by weight; at least about 90% by weight; at least about 95% by weight; at least about 97% by weight; or at least about 99% by weight.

The composition can, in some embodiments, exhibit electrical conductivity. For example, the composition can exhibit a conductivity of about 1×10⁻⁹ S·cm⁻¹. In some embodiments, the composition can exhibit a conductivity of about 1×10⁻¹⁰ S·cm⁻¹ to about 1×10⁻⁵ S·cm⁻¹. The composition can, in some embodiments, exhibit electrical conductivity when doped with an effective amount of dopant. For example, the composition can exhibit a conductivity of about 2.3×10⁻³ S·cm⁻¹ when doped with iodine vapor. In some embodiments, the composition exhibits a conductivity of at least about 10⁻⁸ S×cm¹ when doped with an effective amount of dopant. In some embodiments, the composition exhibits a conductivity of at least about 10⁻⁷ S·cm⁻¹ when doped with an effective amount of dopant. In some embodiments, the composition exhibits a conductivity of at least about 10⁻⁶ S·cm⁻¹ when doped with an effective amount of dopant. In some embodiments, the composition exhibits a conductivity of at least about 10⁻⁵ S·cm⁻¹ when doped with an effective amount of dopant. In some embodiments, the composition exhibits a conductivity of at least about 10⁻³ S·cm⁻¹ when doped with an effective amount of dopant. In some embodiments, the composition exhibits a conductivity of at least about 10⁻² S·cm⁻¹ when doped with an effective amount of dopant. Non-limiting examples of dopants include halogenated compounds, such as iodine, bromine, chlorine, iodine trichloride; protonic acids such as sulfuric acid, hydrochloric acid, nitric acid, perchloric acid; Lewis acids, such as aluminum trichloride, ferric trichloride, molybdenum chloride; and organic acids, such acetic acid, trifluoracetic acid, and benzenesulfonic acid. In some embodiments, the dopant is iodine.

The composition can also exhibit fluorescence when exposed to radiation. In some embodiments, the composition can exhibit green or blue emission when exposed to blue or ultraviolet radiation. The green or blue emission can, for example, have a wavelength of peak emission of about 380 nm to about 650 nm. In some embodiments, the green or blue emission has a wavelength of peak emission of about 475 nm to about 525 nm. The blue or ultraviolet radiation may, for example, have a peak wavelength of about 380 nm to about 450 nm. Specific examples of peak emission wavelengths include about 380 nm, about 390 nm, about 400 nm, about 410 nm, about 420 nm, about 430 nm, about 440 nm, about 450 nm, about 460 nm, about 470 nm, about 480 nm, about 490 nm, about 500 nm, about 510 nm, about 520 nm, about 530 nm, about 540 nm, about 550 nm, about 560 nm, about 570 nm, about 580 nm, about 590 nm, about 600 nm, about 610 nm, about 620 nm, about 630 nm, about 640 nm, about 650 nm, and ranges between any two of these values.

Method of Making Compositions including Polyanthrylene

Some embodiments disclosed herein include a method of making one or more polyanthrylenes. Any one or more of the polyanthrylenes described in the present application can be prepared using this process. The method can include, for example, forming a composition comprising at least one oxidizing agent, at least one co-catalyst and anthracene; and maintaining the composition under conditions effective to covalently bond two or more anthracenes to form one or more polyanthrylenes.

The operation of forming the composition is not particularly limited. Any suitable method of combining the ingredients is within the scope of the present application. For example, the oxidizing agent can be combined (e.g., mixed or dissolved) in a first solvent, and anthracene can be combined (e.g., mixed or dissolved) in a second solvent. The solution can then be combined by dropwise or continuous addition of one of the mixtures to the other. The first and second solvents can be the same or different. In some embodiments, the first solvent is at least partially immiscible in the second solvent. In some embodiments, the oxidizing agent is soluble in the first solvent. In some embodiments, anthracene is soluble in both the first and second solvents. Non-limiting examples for the first solvent include CH₃NO₂, C₆H₅NO₂, CHCl₃, and mixture thereof. Non-limiting examples for the second solvent include nitro-alkane, halogenated alkane, alkane, and mixture thereof. In some embodiments, the second solvent can be CH₃NO₂, n-Hexane, CH₃CH₂NO₂, CH₃CH₂Cl₂, and mixture thereof.

Without being bound to any particular theory, it is believed that the polyanthrylene is formed by dehydrogen coupling between two or more anthracenes. Thus, oxidative agents that can dehydrogenate and dissolve in the solvent system (e.g., CH₃NO₂—CH₂Cl₂) without excessive side-reactions could be selected as the oxidizing agent. In some embodiments, the oxidizing agent is a Lewis acid. Examples of suitable oxidizing agents include, but are not limited to, FeCl₃, AlCl₃—CuCl₂, TiCl₄, MoCl₅, SbCl₅, AsF₅, and any combination thereof.

In some embodiments, the co-catalyst can be the solvent in which the polymerization of anthracene occurs, such as nitro-alkane, halogenated alkane, alkane, or mixture thereof. In some embodiments, the co-catalyst can be CH₃NO₂, n-hexane, CH₃CH₂NO₂, CH₃CH₂Cl₂, or mixture thereof. In some embodiments, the co-catalyst can be CH₂Cl₂—CH₃NO₂. Without being bound to any particular theory, it is believed that Lewis acids can act as an oxidizing agent as well as a co-catalyst in the polymerization of anthracene.

The molar ratio of the oxidizing agent to anthracene in the composition can be, for example, at least about 1:1; at least about 2:1; at least about 3:1; at least about 4:1; at least about 5:1; at least about 7:1; at least about 8:1; at least about 9:1; at least about 10:1; at least about 11:1; at least about 12:1; at least about 13:1; at least about 14:1; at least about 15:1; at least about 16:1; at least about 17:1; or at least about 18:1. The molar ratio of the oxidizing agent to the total amount of anthracene in the composition can be, for example, less than or equal to about 20:1; less than equal to about 15:1; less than or equal to about 12:1; less than equal to about 9:1; less than equal to about 6:1; less than equal to about 3:1; or less than equal to about 1:1. In some embodiments, the molar ratio of the oxidizing agent to anthracene in the composition is about 7:1 to about 9:1.

In some embodiments, at least about 90% by weight of the total amount of aromatic compounds in the composition are anthracene. In some embodiments, at least about 95% by weight of the total amount of aromatic compounds in the composition are anthracene. In some embodiments, at least about 99% by weight of the total amount of aromatic compounds in the composition are anthracene. In some embodiments, substantially all of the total amount of aromatic compounds in the composition is anthracene.

After forming the composition having the oxidizing agent and anthracene, the composition can be maintained at conditions effective to form polyanthrylene. For example, the composition can be maintained at about atmospheric pressure and a temperature of about 10° C. to about 80° C. In some embodiments, the temperature can be about 10° C. to about 60° C. In some embodiments, the temperature can be about 15° C. to about 50° C. Non-limiting examples of the temperature include about 10° C., about 15° C., about 20° C., about 25° C., about 30° C., about 35° C., about 40° C., about 45° C., about 50° C., about 55° C., about 60° C., about 65° C., about 70° C., about 75° C., about 80° C., and ranges between any two of these values. In some embodiments, the temperature can be about 20° C.

The composition can be maintained at the conditions for a period of time sufficient to obtain polyanthrylene. The composition, for example, can be maintained at the conditions for at least about 0.1 hour, at least about 0.5 hour, at least about 1 hour; at least about 3 hours; at least about 5 hours; at least about 10 hours; at least about 15 hours; at least about 20 hours; at least about 24 hours; or longer. The composition, for example, can be maintained at the conditions for less than or equal to about 100 hours; less than or equal to about 50 hours; less than or equal to about 30 hours; less than or equal to about 20 hours, less than or equal to about 10 hours, or less than or equal to about 5 hours.

The method can also optionally include isolating the polyanthrylene from the composition. For example, the polyanthrylene can be isolated by centrifuging the composition to obtain one or more polyanthrylenes within the precipitate. The polyanthrylene can be subject to various other optional treatments, such as washing, doping, dedoping, and the like.

The yield of the one or more polyanthrylenes using the method will vary depending upon various factors, such as the temperature and the like. In some embodiments, the method yields at least about 40% by weight of the one or more polyanthrylenes relative to a total amount of anthracene in the composition. In some embodiments, the method yields at least about 60% by weight of the one or more polyanthrylenes relative to a total amount of anthracene in the composition. In some embodiments, the method yields at least about 70% by weight of the one or more polyanthrylenes relative to a total amount of anthracene in the composition. In some embodiments, the method yields at least about 80% by weight of the one or more polyanthrylenes relative to a total amount of anthracene in the composition.

Methods and Apparatuses for Emitting Light

Some embodiments of the present application include methods and apparatuses for producing light.

A method of producing light can include exposing a composition to a blue or ultraviolet radiation, where the composition includes one or more polyanthrylenes. The method of producing light can include any one or more of the compositions described in this application. The blue or ultraviolet radiation can, for example, have a peak wavelength of about 380 nm to about 650 nm. In some embodiments, the method produces blue or green light. For example, the blue or green emission can have a wavelength of peak emission of about 380 nm to about 550 nm. In some embodiments, the blue or green emission can have a wavelength of peak emission of about 475 nm to about 525 nm. Specific examples of peak wavelengths include about 380 nm, about 390 nm, about 400 nm, about 410 nm, about 420 nm, about 430 nm, about 440 nm, about 450 nm, about 460 nm, about 470 nm, about 480 nm, about 490 nm, about 500 nm, about 510 nm, about 520 nm, about 530 nm, about 540 nm, about 550 nm, about 560 nm, about 570 nm, about 580 nm, about 590 nm, about 600 nm, about 610 nm, about 620 nm, about 630 nm, about 640 nm, about 650 nm, and ranges between any two of these values.

FIG. 1 depicts an illustrative embodiment of a lighting apparatus that is within the scope of the present application. Lighting apparatus 100 includes substrate 110 having a light source 120 disposed above substrate 110. The light source can be coupled to an electric source and configured to emit blue or ultraviolet radiation. For example, the light source can be an indium gallium nitride (InGaN) semiconductor, ultraviolet bulb, and ultraviolet laser (e.g., He—Cd laser, N, laser, and Kr/Ar ion laser). Composition 130 is disposed next to light source 120 and configured to receive at least a portion of the radiation from light source 120. Composition 130 can be a powder dispersed in encapsulant resin 140. For example, encapsulant resin 140 can be an epoxy. As an alternative, the composition can be a film disposed above the light source (not shown).

In some embodiments, the apparatus includes: a light source configured to emit an ultraviolet or blue radiation; and a composition configured to receive at least a portion of the radiation emitted from the light source, where the composition includes one or more polyanthrylenes. The composition can include one or more polyanthrylenes as described in the present application.

The polyanthrylene compositions of the present application can also be included in an organic light emitting diode (OLED) OLEDs are well-known in the art. For example, U.S. Pat. No. 6,322,910 discloses various configurations for OLEDs. A typical OLED can include a light emitting layer disposed between a cathode and anode. A current flow between the cathode and anode can result in electrons recombining with electron holes in the light emitting layer. This recombination can result in emission. Thus, for example, the light emitting layer can include any one or more of the polyanthrylene compositions described in the present application. In some embodiments, the OLED can include multiple emissive layers.

FIG. 2 is an illustrative embodiment of an organic light emitting diode that is within the scope of the present application. OLED 200 includes anode 210 having conducting layer 220 above anode 210. Emissive layer 230 is disposed between conductive layer 220 and cathode 240. The anode can be, for example, indium tin oxide (ITO), which can optionally be disposed on a transparent substrate (e.g., glass) (not shown). Meanwhile, metals with low work functions, such as barium or calcium, can be used to form the cathode. The conductive layer can be a conductive polymer, such as poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS). The emissive layer can include any one or more of the polyanthrylene compositions described in the present application.

Methods and Apparatuses for Detecting Iron

Some embodiments of the present application include methods and apparatuses for detecting iron, for example ferrous ions (sometimes written as Fe(II) or Fe²⁺) or ferric ions (sometimes written as Fe(III) or Fe³⁺) from a sample. Without being bound to any particular theory, it is believed that ferrous ions in aqueous solution are unstable and can be easily and quickly oxidized into ferric ions by oxygen in the air, and ferric ions can quench fluorescence of the polyanthrylene compositions described in the present application. Thus, if the composition exhibits reduced fluorescence, this can be correlated with exposing the composition to iron, for example a ferric ion (Fe(III)) or a ferrous ion (Fe(II)).

In some embodiments, a method for detecting ferric ions includes: (a) providing a sample suspected of containing one or more ferric ions; (b) contacting the sample with a composition having one or more polyanthrylenes to form a mixture; (c) exposing the mixture to a radiation effective to produce fluorescence from the mixture; and (d) measuring the amount of fluorescence produced by the mixture. The composition can be any one or more of the polyanthrylene compositions described in the present application. For example, the composition can include the compound of Formula XVIII, the compound represented by Formula XIX, the compound represented by Formula XX, the compound of Formula XXI, the compound of Formula XXII, the compound of Formula XXIII, the compound of Formula XXV, the compound of Formula XXVI, the compound of Formula XXVII, and the compound of Formula XXVIII disclosed above.

In some embodiments, the produced fluorescence is greater in the absence of iron than in the presence of iron. In some embodiments, the produced fluorescence is greater in the absence of ferric ions than in the presence of ferric ions. The fluorescence can be measured, for example, by measuring the fluorescence intensity at a pre-determined color or wavelength. For example, the intensity of emission at a wavelength of about 502 nm can be measured. In some embodiments, the radiation effective to produce fluorescence from the composition is a blue or ultraviolet radiation.

FIG. 3 depicts an illustrative embodiment of an apparatus for detecting ferric ions that is within the scope of the present application. Apparatus 300 can include housing 310 that contains composition 320, light source 330, light detector 340, and port 350. Composition 320 can include any one or more of the polyanthrylene compositions described in the present application. Light source 330 is configured to emit radiation effective to produce fluorescence from copolymer film 320. For example, light source 330 can be an InGaN semiconductor that emits blue or ultraviolet radiation. Light detector 340 can be configured to measure light emission from composition 320. Port 350 can be configured to receive a sample into the housing. Thus, for example, a sample suspected of containing one or more ferric ions can be placed into housing 310 via port 350, so that the sample contacts composition 320. Light source 330 can then emit light and the fluorescence from composition 320 is detected by light detector 340. The amount of fluorescence can then be correlated with the presence of ferric ions in the sample.

In some embodiments, the apparatus for detecting iron, such as ferric ions, includes a processor coupled to at least the light source and light detector (not shown). The processor can be configured to synchronize both emitting light from the light source and detecting fluorescence with the light detector. The processor can also receive measurement data from the light detector and automatically correlate this data with the presence of iron, such as ferric ions.

Various concentrations of iron, such as ferric ions, can be detected by any one or more of the polyanthrylene compositions described in the present application. In some embodiments, the sample is an aqueous sample. In some embodiments, the sample is an environmental sample. In some embodiments, the sample is ocean water. The concentration of the ferric ion in the sample can be from about 10⁻⁹ mol/L (i.e., 10⁻⁹ M) to about 10⁻³ M, from about 10⁻⁹ M to about 10⁻⁴ M, from about 10⁻⁸ M to about 10⁻⁵ M, from about 10⁻⁷ M to about 10⁻⁶ M, and ranges between any two of these values. In some embodiments, the concentration of the ferric iron in the sample is no more than about 10⁻⁴ M. In some embodiments, the concentration of the ferric ion is no more than about 10⁻⁶ M. In some embodiments, the concentration of the ferric ion in the sample is less than about 10⁻⁷ M. In some embodiments, the concentration of the ferric ion in the sample is about 10⁻⁸ M. In some embodiments, the concentration of the ferric ion in the sample is about 10⁻⁹ M.

While various aspects and embodiments have been disclosed herein, other aspects and embodiments will be apparent to those skilled in the art. The various aspects and embodiments disclosed herein are for purposes of illustration and are not intended to be limiting, with the true scope and spirit being indicated by the following claims.

One skilled in the art will appreciate that, for this and other processes and methods disclosed herein, the functions performed in the processes and methods can be implemented in differing order. Furthermore, the outlined steps and operations are only provided as examples, and some of the steps and operations can be optional, combined into fewer steps and operations, or expanded into additional steps and operations without detracting from the essence of the disclosed embodiments.

EXAMPLES

Additional embodiments are disclosed in further detail in the following examples, which are not in any way intended to limit the scope of the claims.

Example 1 Preparation of Polyanthrylene (PAn)

The synthesis of polyanthrylene (PAn) was carried out by a chemical oxidative dehydrogenation polymerization of anthracenes (An) in CH₃NO₂—CH₂Cl₂ mixture.

A typical synthesis procedure of PAn included dissolving anthracene (800 mg, 4.49 mmol) in 30 mL CH₂Cl₂ in a conical flask in a water bath at 20° C. An oxidant solution was prepared by dissolving the oxidant FeCl₃ (6552 mg, 40.4 mmol) in 30 mL CH₃NO₂ at 20° C. Next, the oxidant solution was added all at once into the anthracene solution in water bath at 20° C., and the reaction mixture was magnetically stirred at 20° C. for 6 hours. Besides the role of the oxidative agent, FeCl₃ also functioned as a co-catalyst in the polymerization process. The other co-catalyst was CH₃NO₂—CH₂Cl₂ which was also used as the solvent for polymerization reaction. The polymerization was terminated by adding 60 mL ethanol to the reaction mixture. The polymer particles were precipitated and isolated from the reaction mixture by a centrifugal precipitation method, and then washed repeatedly with 95% ethanol until the filtrate became colorless. The polymer particles were subsequently washed with deionized water until the filtrate showed negative in a test for Fe(III) and Fe(II) ions by using 100 mM K₄Fe(CN)₆ and 50 mM K₃Fe(CN)₆ as color indicators, respectively. The dark brown powder as a virgin PAn salt was obtained after drying under air atmosphere at 80° C. For the purpose of removing of possible dopant impurities, the virgin PAn salt was washed successively with 1 M HCl solution, deionized water, 200 mM aqueous ammonia and deionized water, again until a negative test for Fe(III) and Fe(II) was obtained. The de-doped polymer particles as a pure PAn base were left to dry under air atmosphere at 80° C. for 3 days, giving a synthetic yield of 66.3%. Iodine vapor doping was carried out in closed graded tube (5 mL) containing 30 mg powdered virgin PAn and 150 mg solid iodine at a constant temperature of 80° C. under atmospheric pressure for a whole day. Direct contact between the PAn powders and the iodine particles was avoided.

The anthracene polymerization was followed by an open circuit potential (OCP) in situ tracking method using a saturated calomel electrode (SCE) and a platinum sheet electrode as the reference electrode and the working electrode respectively.

Example 2 UV-Vis, Fluorescence Excitation and Emission Spectra

PAn particles were prepared according to Example 1. UV-vis and fluorescence spectra of those PAn particles at a concentration of 20 mg/L in N-methyl-2-pyrrolidone (NMP) aqueous medium were respectively recorded by using a 760CRT double-beam UV-vis spectrophotometer and a 970CRT fluorospectrophotometer. These results are shown in FIGS. 4 a-c.

FIG. 4 a shows the large difference between the UV-vis spectra of anthracene and that of PAn. The broad emission band exhibited by PAn with a maximum at 504 nm (excited at 380 nm) and a large Stokes shift of 117 nm demonstrates a rigid semi-ladder structure of PAn (see FIGS. 4 b-c). Moreover, PAn showed 1.70 times stronger emission and 2.70 times higher Stokes shift than anthracene which emits only blue light, demonstrating that PAn is a strong green emitter with a high Stokes shift, and thus can be useful as a naked-eye fluorescent sensor.

Furthermore, it was found that the PAn prepared was a strong color light emitter that emitted blue light in low dielectric constant solvents including n-hexane, benzene, n-butanol, THF, ethanol, and chloroform. Also, the PAn was observed to emit green light in high dielectric constant solvents such as acetone, NMP, DMF, and DMSO.

Example 3 MALDI-TOF Mass Spectra

PAn particles were prepared with oxidant FeCl₃/anthracene molar ratio of 9:1 according to the general procedure described in Example 1. The matrix assistant laser desorption ionization time of flight mass spectrum (MALDI-TOF MS) of those PAn particles was recorded on a Waters Micromass MALDI micro MX mass spectrometer with sinapinic acid as matrix. The results are shown in FIG. 5. Structural assignments of the peaks appearing in the MALDI-TOF mass spectra of the PAn are shown in Table 1, demonstrating that the obtained PAn is composed of 3 to 11 repeat anthrylene units containing semi-ladder structures.

TABLE 1 Structural assignments of the peaks appearing in the MALDI-TOF mass spectra of the PAn Repeat unit m/z n Possible structures 526.5 3

703 4

866.9 5

1581.4 9

1758.0 10

1932.0 11

Example 4 NMR Spectra

PAn particles were prepared according to Example 1. ¹H 1D and ¹H—¹H COSY 2D NMR spectra of the soluble portion of those PAn particles in DMSO-d6 were determined using a Bruker DQX-400 spectrometer. The results are shown in FIG. 6.

The PAn displayed much more complicated ¹H NMR and ¹H—¹H COSY NMR spectra than anthracene. For example, there were two cross peaks in the ¹H—¹H 2D COSY spectrum of the PAn (FIG. 6 a) as compared to a single cross peak in that of anthracene (FIG. 6 b). The much weaker resonance peak due to γ-H in the ¹H NMR spectrum of the PAn shown in FIG. 6 c demonstrates that the oxidative coupling of anthracene rings occurred mainly at γ positions (9,10-positions). An additional weak cross peak (8.27, 8.80 ppm) shown in FIG. 6 c further shows that the oxidative coupling of anthracene rings also occurred partly at α positions (1,4,5,8-positions), forming a semi-ladder structure.

Example 5 Elemental Analysis

PAn particles were prepared according to Example 1. The elemental analysis of those PAn particles was carried out using a VARIO EL3 elemental microanalyzer.

Elemental analysis showed that the C/H atomic ratio in the PAn was 1.79, which was larger than the C/H ratio of 1.75 for linear PAn (—C₁₄H₈—)_(n), indicating the existence of a semi-ladder structure in the PAn molecules.

Example 6 Electrical Conductivity

PAn particles were prepared according to Example 1. The bulk electrical conductivity of the PAn was measured from pressed pellets according to the two-electrode method on a UT70A multimeter at ambient temperature. The electrical conductivity for virgin PAn salt was determined to be 1.00×10⁻⁹ S·cm⁻¹, and the electrical conductivity for iodine-doping PAn salt was determined to be 2.30×10⁻³ S·cm⁻¹.

Example 7 Fluorescence Emission

PAn particles were prepared according to Example 1. Fluorescence emission spectra of those PAn particles at a concentration of 10 mg/L, 20 mg/L, 45 mg/L, 60 mg/L or 90 mg/L in N-methyl-2-pyrrolidone (NMP) aqueous medium were respectively recorded using a 970CRT fluorospectrophotometer. The results are shown in FIG. 7.

This example shows that fluorescence emission intensity of the PAn solution depends on its concentration, and the strongest fluorescence emitting by the PAn solution in the concentration tested is in the concentration of 20 mg/L.

Example 8 Fluorescence Spectral Responses of PAn To Fe(III)

PAn particles were prepared according to Example 1. Those PAn particles were dissolved in NMP solution to make a PAn-NMP solution with the concentration of PAn at 25 mg/L. 4 mL of the PAn-NMP solution (the concentration of PAn at 25 mg/L) was mixed with 1 mL Fe(III) aqueous solution at a given concentration and the mixture solution was allowed to stand for 5 minutes at ambient temperature before a fluorescence measurement was performed. Using a constant excitation at 380 nm, the fluorescence emission intensity at 502 nm was used to establish a linear quantitative relation to the Fe(III) concentration for facilely sensing Fe(III). The results are shown in FIGS. 8-9.

FIG. 8 shows that the fluorescent emission intensity of the PAn only slightly reduced when 10˜20 vol % water was added into the PAn-NMP solution, demonstrating that the fluorescent emission of the PAn is insensitive to a small amount of water in the solution system.

FIG. 9 shows a quenching effect on the addition of ferric ion. For example, the quenching ratios (1−I/I₀)×100% of PAn fell between 1.47% and 92.8%, with no noticeable shift in its λ_(max) of 502 nm as the Fe(III) concentration increased from 1.00×10⁻⁹ to 1.00×10⁻³ M. FIG. 9 inset further shows that in the Fe(III) concentration range of 0 μM to 1000 μM, a satisfactory linear correlation could be fitted, with a correlation coefficient R of 0.99651. These results demonstrate the exceptional sensitivity of the PAn-based chemosensor system in detection of ferric ions is at an ultralow nanomolar level (down to 1.00×10⁻⁹ M).

Example 9 Ion Selectivity of PAn

PAn particles were prepared according to Example 1. Those PAn particles were dissolved in NMP solution to make a PAn-NMP solution with the concentration of PAn at 20 mg/L.

Potential Interfering Ions at Concentration of 1 Mm

Solutions of various metal salts were prepared to investigate potential interferences in the detection of Fe(III) using PAn. Sixteen types of ions: H⁺, Na(I), K(I), Ca(II), Mn(II), Co(II), Ni(II), Cu(II), Ag(I), Cd(II), Ba(II), Hg(II), Pb(II), Cl⁻, NO₃ ⁻, and SO₄ ²⁻, at the concentration of 1 mM in the PAn-NMP solutions, were individually used to evaluate the ion selectivity of the PAn-based chemosensor. The variation of the fluorescence emission intensity of PAn-NMP solution containing a mixture of Fe(III) and those 16 types of ions was measured to evaluate the interference caused by those ions in the detection of Fe(III) ions. The degree of interference was evaluated by 502 nm intensity variation of corresponding fluorescence emission spectra. The results are shown in FIG. 10.

TABLE 2 The quenching degree and charge density of various types of cations to the PAn-based chemosensor Metal ion H(I) Na(I) K(I) Ca(II) Mn(II) Fe(III) Co(II) Quenching degree/% 0 0 0 0.722 0.722 93.2 38.3 I₀/I 0 0 0.00379 1.007 1.007 14.62 1.62 Charge density/(Per 1.91 0.26 0.1 0.49 0.93 4.31 1.28 Angstrom³) Metal ion Ni(II) Cu(II) Ag(I) Cd(II) Ba(II) Hg(II) Pb(II) Quenching degree/% 2.90 8.71 0.722 0.355 0.722 1.82 5.95 I₀/I 1.03 1.095 1.007 1.004 1.007 1.019 1.063 Charge density/(Per 1.45 1.28 0.12 0.52 0.2 0.36 0.21 Angstrom³)

FIG. 10 shows that H⁺, Na(I), K(I), Ca(II), Mn(II), Ni(II), Cu(II), Ag(I), Cd(II), Ba(II), Hg(II), Pb(II), Cl⁻, NO₃ ⁻, and SO₄ ²⁻ had no noticeable response to the fluorescence signal, and only Co(II) produced a slight quench. Accordingly, it demonstrates that the PAn chemosensor displays not only a highly sensitive fluorescence quenching response to Fe(III), but also an excellent selectivity against many metal ions, including Cu(II).

Interfering Effects of Co(II), Na(I), Ca(II) and Mg(II)

The fluorescent quenching strength of a solution mixture of Co(II) (0.1 mM) and Fe(III) (0.1 mM) were measured. The results are shown in FIG. 11 a. It was surprising that the co-existent Co(II) at the same concentration as the target ion Fe(III) resulted in negligible fluorescent and absorbance intensity change at 502 nm in almost the whole wavelength range, respectively, demonstrating that Co(II) does not significantly interfere with Fe(III) detection during the competition quenching process.

Similar measurements were conducted for two solutions with mixed Fe(III), Na(I), Ca(II) and Mg(II). In both solutions, the concentration of Fe(III) was 0.1 mM, whereas the concentration of each of the other ions (i.e., Na(I), Ca(II) and Mg(II)) is 0.1 mM in one solution and 1 mM in the other solution. The results are shown in FIG. 11 b. FIG. 11 b shows there is little fluorescent or absorbance change even if the concentration of Na(I), Ca(II) and Mg(II) ions are 10,000 times higher than that of Fe(III), demonstrating that the PAn has remarkably high selectivity towards Fe(III) and an excellent anti-interference ability against other metal ions.

Example 10 Detection of Fe(II) in Environmental Samples

PAn particles were prepared according to Example 1. Those PAn particles were used to detect iron content in environmental samples. Tap water was collected from an indoor tap in Tongji University, Shanghai, China. Residual water in the water pipe was discharged before collecting tap water for fluorescence quenching experiments without any pretreatment. River water sample was collected from the small river in the same university grounds and filtered three times to completely remove suspended solids and sediments. The concentration of various metal ions including Fe(III), Na(I), Ca(II), Cu(II), Zn(II), Cd(II), Hg(II) and Pb(II) in the water samples was determined by analyzing fluorescence spectra (excited at 380 nm) for the solution of PAn (20 mg/L) in NMP-water (4:1, v/v) after addition of pure water and actual water samples by a calibration curve obtained by this PAn chemosensor. To verify the sensitivity and accuracy of the results obtained by the PAn chemosensor, the concentration of the various metal ions were also determined using the inductively coupled plasma mass spectroscopy (ICP-MS) method which is presently one of the common methods for iron determination. The results are shown in Tables 3 and 4.

TABLE 3 The content of various metal ions (μM) in water samples measured by ICP-MS Water sample Na(I) Ca(II) Fe(III) Cu(II) Zn(II) Cd(II) Hg(II) Pb(II) Tap water 1683 1073 3.44 1.10 5.31 0.089 <0.15 <0.121 River water 5174 1870 0.897 0.853 1.56 <0.018 <0.15 <0.121

TABLE 4 Concentration of Fe(III) in water samples (3 replicates) Concentration of Fe^(III) (μM) determined by Fluorescence quenching using PAn Sample 1^(st) 2^(nd) 3^(rd) Average ICP-MS Relative error (%) Tap water 3.43 3.42 3.38 3.41 3.44 −0.87 River water 0.910 0.907 0.929 0.915 0.897 2.04

As shown in Table 3, including Fe(III), a total of eight types of metal ions were detected in the water samples. Table 4 shows that the Fe(III) concentrations measured using PAn chemosensor were virtually identical to those detected by ICP-MS methods with very little relative error (−0.87%˜2.04%) despite the existence of seven other metal ions in the water samples. Accordingly, this example shows that the PAn chemosensor can provide accurate and selective analysis of Fe(III) in water samples.

With respect to the use of substantially any plural and/or singular terms herein, those having skill in the art can translate from the plural to the singular and/or from the singular to the plural as is appropriate to the context and/or application. The various singular/plural permutations may be expressly set forth herein for sake of clarity.

It will be understood by those within the art that, in general, terms used herein, and especially in the appended claims (e.g., bodies of the appended claims) are generally intended as “open” terms (e.g., the term “including” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “having at least,” the term “includes” should be interpreted as “includes but is not limited to,” etc.). It will be further understood by those within the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present. For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases “at least one” and “one or more” to introduce claim recitations. However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles “a” or “an” limits any particular claim containing such introduced claim recitation to embodiments containing only one such recitation, even when the same claim includes the introductory phrases “one or more” or “at least one” and indefinite articles such as “a” or “an” (e.g., “a” and/or “an” should be interpreted to mean “at least one” or “one or more”); the same holds true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should be interpreted to mean at least the recited number (e.g., the bare recitation of “two recitations,” without other modifiers, means at least two recitations, or two or more recitations). Furthermore, in those instances where a convention analogous to “at least one of A, B, and C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “a system having at least one of A, B, and C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, etc.). In those instances where a convention analogous to “at least one of A, B, or C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., a system having at least one of A, B, or C″ would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, etc.). It will be further understood by those within the art that virtually any disjunctive word and/or phrase presenting two or more alternative terms, whether in the description, claims, or drawings, should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phrase “A or B” will be understood to include the possibilities of “A” or “B” or “A and B.”

In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

As will be understood by one skilled in the art, for any and all purposes, such as in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as “up to,” “at least,” and the like include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member. Thus, for example, a group having 1-3 cells refers to groups having 1, 2, or 3 cells. Similarly, a group having 1-5 cells refers to groups having 1, 2, 3, 4, or 5 cells, and so forth.

From the foregoing, it will be appreciated that various embodiments of the present disclosure have been described herein for purposes of illustration, and that various modifications may be made without departing from the scope and spirit of the present disclosure. Accordingly, the various embodiments disclosed herein are not intended to be limiting, with the true scope and spirit being indicated by the following claims. 

What is claimed is:
 1. A method of making a copolymer, the method comprising: forming a mixed solution comprising at least one oxidizing agent, at least one co-catalyst and anthracenes; maintaining the mixed solution under conditions effective to covalently bond two or more anthracenes to form one or more polyanthrylenes; wherein the one or more polyanthrylenes form particles; and isolating the polyanthrylene particles from the mixed solution, wherein the one or more polyanthrylenes each independently comprises at least two monomer units each independently represented by a formula selected from the group consisting of Formula I, Formula II, Formula III, Formula IV, Formula V, Formula VI, Formula VII, Formula VIII, Formula IX, Formula X, Formula XI, Formula XII, Formula XIII, Formula XIV, Formula XV, Formula XVI, Formula XVII, and any combination thereof:

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷, R³⁸, R³⁹, R⁴⁰, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷, R⁴⁸, R⁴⁹, R⁵⁰, R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷, R⁵⁸, R⁵⁹, R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, R⁶⁶, R⁶⁷, and R⁶⁸ are each independently hydrogen or an electron donating group; and wherein at least one monomer unit in the one or more polyanthrylenes is not represented by Formula I.
 2. The method of claim 1, wherein the co-catalyst is selected from the group consisting of a nitro-alkane, a halogenated alkane, an alkane, and a mixture thereof.
 3. The method of claim 1, wherein the maintaining step is performed at a temperature of 10° C. to 80° C.
 4. The method of claim 1, wherein at least one of the one or more polyanthrylenes has a molecular formula selected from the group consisting of C₄₂H₂₂, C₅₆H₃₀, C₇₀H₂₆, C₁₂₆H₆₈, C₁₄₀H₇₈, and C₁₅₄H₈₄.
 5. The method of claim 1, wherein at least 90% by weight of a total amount of aromatic organic compounds in the composition are polyanthrylene.
 6. The method of claim 1, wherein the molar ratio of the oxidizing agent to anthracene in the composition is less than or equal to 18:1.
 7. The method of claim 6, wherein the molar ratio of the oxidizing agent to anthracene in the composition is from 7:1 to 9:1.
 8. The method of claim 1, wherein the oxidizing agent is a Lewis acid.
 9. The method of claim 8, wherein the Lewis acid is selected from the group consisting of FeCl₃, AlCl₃—CuCl₂, TiCl₄, MoCl₅, SbCl₅, AsF₅, and any combination thereof.
 10. The method of claim 1, wherein the co-catalyst is selected from the group consisting of CH₃NO₂, CH₂Cl₂, n-Hexane, CH₃CH₂NO₂, CH₃CH₂Cl₂, and a mixture thereof.
 11. The method of claim 10, wherein the co-catalyst is CH₃NO₂, CH₂Cl₂, n-hexane, or a mixture thereof. 